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Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid

Bonjour, Olivier LU ; Liblikas, Ilme ; Pehk, Tõnis ; Truong, Khai-Nghi ; Rissanen, Kari ; Vares, Lauri and Jannasch, Patric LU (2020) In Green Chemistry 22(12). p.3940-3951
Abstract
Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone (cis-bicyclo[3.3.0]octane-3,7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the usefulness of the new monomer, it was employed in melt... (More)
Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone (cis-bicyclo[3.3.0]octane-3,7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the usefulness of the new monomer, it was employed in melt polycondensations with diphenylcarbonate at up to 280 °C to form rigid fully amorphous polycarbonates (PCs). Molecular weights (MWs) up to Mn = 28 kg mol-1 were achieved, and thermal and dynamic mechanical measurements showed glass transitions up to Tg = 100 °C, with no thermal decomposition until Td ~ 350 °C. Solvent cast films had excellent mechanical flexibility and strength, as well as a high transparency with only slight coloration. Results by dynamic melt rheology implied that the high-MW PCs had a good processability at 170 °C, with a stable shear modulus over time, but started to degrade via chain scission reactions when the temperature approached 200 °C. In conclusion, the present work demonstrates the straightforward preparation of the citric acid-based spiro-diol, and indicates that it is an efficient building block for the preparation of rigid biobased PCs and other condensation polymers. (Less)
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author
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organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Green Chemistry
volume
22
issue
12
pages
12 pages
publisher
Royal Society of Chemistry
external identifiers
  • scopus:85087624471
ISSN
1463-9270
DOI
10.1039/D0GC00849D
language
English
LU publication?
yes
additional info
Submitted: 09 Mar 2020 Accepted: 27 May 2020 First published: 28 May 2020
id
3dc8f324-9e89-4c2d-a6be-71f2dfbdcf06
date added to LUP
2020-05-27 15:50:22
date last changed
2020-07-29 06:14:53
@article{3dc8f324-9e89-4c2d-a6be-71f2dfbdcf06,
  abstract     = {Introducing biobased polymers from renewable sources for use as high-performance thermoplastics with high demands on mechanical rigidity, transparency, thermal stability, as well as good processability, is a significant challenge. In the present work we have designed and prepared a rigid biobased bis-spirocylic diol by di-cycloketalization of a bicyclic diketone (cis-bicyclo[3.3.0]octane-3,7-dione, obtained from citric acid) using trimethylolpropane. This spiro-diol monomer has two reactive primary hydroxyl groups and the synthesis from inexpensive biobased starting materials is straightforward and readily upscalable, involving no chromatographic purification. In order to explore the usefulness of the new monomer, it was employed in melt polycondensations with diphenylcarbonate at up to 280 °C to form rigid fully amorphous polycarbonates (PCs). Molecular weights (MWs) up to <i>M</i><sub>n</sub> = 28 kg mol-1 were achieved, and thermal and dynamic mechanical measurements showed glass transitions up to <i>T</i><sub>g</sub> = 100 °C, with no thermal decomposition until <i>T</i><sub>d</sub> ~ 350 °C. Solvent cast films had excellent mechanical flexibility and strength, as well as a high transparency with only slight coloration. Results by dynamic melt rheology implied that the high-MW PCs had a good processability at 170 °C, with a stable shear modulus over time, but started to degrade via chain scission reactions when the temperature approached 200 °C. In conclusion, the present work demonstrates the straightforward preparation of the citric acid-based spiro-diol, and indicates that it is an efficient building block for the preparation of rigid biobased PCs and other condensation polymers.},
  author       = {Bonjour, Olivier and Liblikas, Ilme and Pehk, Tõnis and Truong, Khai-Nghi and Rissanen, Kari and Vares, Lauri and Jannasch, Patric},
  issn         = {1463-9270},
  language     = {eng},
  number       = {12},
  pages        = {3940--3951},
  publisher    = {Royal Society of Chemistry},
  series       = {Green Chemistry},
  title        = {Rigid biobased polycarbonates with good processability based on a spirocyclic diol derived from citric acid},
  url          = {http://dx.doi.org/10.1039/D0GC00849D},
  doi          = {10.1039/D0GC00849D},
  volume       = {22},
  year         = {2020},
}